EP3890063A1 - Matériau d'électrode négative et batterie - Google Patents

Matériau d'électrode négative et batterie Download PDF

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Publication number
EP3890063A1
EP3890063A1 EP19888701.0A EP19888701A EP3890063A1 EP 3890063 A1 EP3890063 A1 EP 3890063A1 EP 19888701 A EP19888701 A EP 19888701A EP 3890063 A1 EP3890063 A1 EP 3890063A1
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Prior art keywords
solid electrolyte
negative electrode
electrolyte material
electrode material
battery
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German (de)
English (en)
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EP3890063A4 (fr
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Tatsuya Oshima
Izuru SASAKI
Seiji Nishiyama
Akira Kawase
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0407—Methods of deposition of the material by coating on an electrolyte layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/582—Halogenides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/008—Halides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present disclosure relates to a negative electrode material and a battery.
  • NPL 1 discloses an all-solid lithium ion battery in which a sulfide solid electrolyte material is used as a negative electrode material.
  • NPL 1 F. Han et al., "A Battery Made from Single Material”, Adv. Mater. 27 (2015), 3473-3483
  • a negative electrode material includes a reduced form of a first solid electrolyte material and a conductive auxiliary, wherein the first solid electrolyte material is denoted by Formula (1) below, Li ⁇ M ⁇ X ⁇ Formula (1) herein, in Formula (1), each of ⁇ , ⁇ , and ⁇ is a value greater than 0, M represents at least one element selected from the group consisting of metal elements except Li and semimetals, and X represents at least one element selected from the group consisting of F, CI, Br, and I.
  • the charge-discharge efficiency of the battery can be improved.
  • a negative electrode material according to the first embodiment contains a reduced form (hereafter also referred to as “halide reduced form”) of a first solid electrolyte material (hereafter also referred to as “halide solid electrolyte material”) and a conductive auxiliary.
  • the halide solid electrolyte material is a material denoted by Formula (1) below. Li ⁇ M ⁇ X ⁇ Formula (1)
  • each of ⁇ , ⁇ , and ⁇ is a value greater than 0.
  • M represents at least one element selected from the group consisting of metal elements except Li and semimetals.
  • X represents at least one element selected from the group consisting of F, CI, Br, and I.
  • “semimetals” include B, Si, Ge, As, Sb, and Te.
  • metal elements include
  • the negative electrode material according to the first embodiment can improve the charge-discharge efficiency of a battery due to the above-described configuration.
  • NPL 1 cited in the section "Background Art” discloses a battery in which the negative electrode material is the reduced form of the sulfide solid electrolyte material (hereafter also referred to as "sulfide reduced form").
  • the present inventors performed intensive research and, as a result, found that a battery in which a sulfide reduced material was used as a negative electrode material had a problem of a reduction in charge-discharge efficiency of the battery because of, for example, low electron conductivity and low ionic conductivity of the sulfide reduced form.
  • the above-described halide reduced form exhibits favorable electron conductivity and favorable ionic conductivity. That is, the negative electrode material according to the first embodiment includes a halide reduced form that exhibits favorable electron conductivity and favorable ionic conductivity and a conductive auxiliary that assists electron conductivity and, therefore, can improve the charge-discharge efficiency of the battery.
  • halide solid electrolyte material in the first embodiment may satisfy
  • the charge-discharge efficiency of the battery can be further improved.
  • m represents the valence of M.
  • m ⁇ is the total of the products of the respective composition ratios of the elements multiplied by the respective valences of the elements.
  • the composition ratio of the element M1 is ⁇ 1
  • the valence of the element M1 is m 1
  • the composition ratio of the element M2 is ⁇ 2
  • the valence of the element M2 is m 2
  • m ⁇ m 1 ⁇ 1 + m 2 ⁇ 2
  • the above-described relational formula has to be satisfied with respect to each of the valences, where m takes on the respective valence.
  • the charge-discharge efficiency of the battery can be further improved.
  • M may contain at least one element selected from the group consisting of transition metal elements.
  • the charge-discharge efficiency of the battery can be further improved.
  • the halide solid electrolyte material containing Y may be denoted by Formula (2) below. Li a Me b Y c X 6 Formula (2)
  • m e represents the valence of Me.
  • Me contains a plurality of types of elements
  • m e b is the total of the products of the respective composition ratios of the elements multiplied by the respective valences of the elements.
  • Me1 may be at least one selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sc, Al, Ga, Bi, Zr, Hf, Ti, Sn, Ta, and Nb.
  • Me may be at least one selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sc, Al, Ga, Bi, Zr, Hf, Ti, Sn, Ta, and Nb.
  • the charge-discharge efficiency of the battery can be further improved.
  • the halide solid electrolyte material in the first embodiment may be a material denoted by Composition formula (3) below.
  • Composition formula (3) Li6-3dYdX6 Formula (3)
  • X represents at least two elements selected from the group consisting of CI, Br, and I.
  • d satisfies 0 ⁇ d ⁇ 2.
  • the negative electrode material according to the first embodiment in the case in which the halide solid electrolyte material satisfies Formula (3), the negative electrode material according to the first embodiment can improve the cycle characteristics of the battery and, in addition, can also improve the charge-discharge efficiency of the battery. Further, since the halide solid electrolyte material that satisfies Formula (3) has high ionic conductivity, a halide reduced form can be efficiently generated.
  • the halide solid electrolyte material according to the first embodiment may be a material denoted by Formula (4) below.
  • Formula (4) Li 3 YX 6 Formula (4)
  • X represents at least two elements selected from the group consisting of CI, Br, and I. That is, in Composition formula (3) above, d may be 1.
  • the negative electrode material according to the first embodiment in the case in which the halide solid electrolyte material satisfies Formula (4), the negative electrode material according to the first embodiment can improve the cycle characteristics of the battery and, in addition, can also improve the charge-discharge efficiency of the battery. Further, since the halide solid electrolyte material that satisfies Formula (4) has high ionic conductivity, a halide reduced form can be efficiently generated.
  • the halide solid electrolyte material according to the first embodiment may be a material denoted by Composition formula (5) below. Li 3-3 ⁇ Y 1+ ⁇ Cl 6 Formula (5)
  • the negative electrode material according to the first embodiment in the case in which the halide solid electrolyte material satisfies Formula (5), the negative electrode material according to the first embodiment can improve the cycle characteristics of the battery and, in addition, can also improve the charge-discharge efficiency of the battery. Further, since the halide solid electrolyte material that satisfies Formula (5) has high ionic conductivity, a halide reduced form can be efficiently generated.
  • the halide solid electrolyte material according to the first embodiment may be a material denoted by Composition formula (6) below. Li 3-3 ⁇ Y 1+ ⁇ Br 6 Formula (6)
  • the negative electrode material according to the first embodiment in the case in which the halide solid electrolyte material satisfies Formula (6), the negative electrode material according to the first embodiment can improve the cycle characteristics of the battery and, in addition, can also improve the charge-discharge efficiency of the battery. Further, since the halide solid electrolyte material that satisfies Formula (6) has high ionic conductivity, a halide reduced form can be efficiently generated.
  • the halide solid electrolyte material in the first embodiment may be a material denoted by Composition formula (7) below. Li 3-3 ⁇ +a Y 1+ ⁇ -a Me a Cl 6-x-y Br x I y Formula (7)
  • Me represents at least one element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn. Further, in Composition formula (7),
  • the negative electrode material according to the first embodiment in the case in which the halide solid electrolyte material satisfies Formula (7), the negative electrode material according to the first embodiment can improve the cycle characteristics of the battery and, in addition, can also improve the charge-discharge efficiency of the battery. Further, since the halide solid electrolyte material that satisfies Formula (7) has high ionic conductivity, a halide reduced form can be efficiently generated.
  • the halide solid electrolyte material in the first embodiment may be a material denoted by Composition formula (8) below. Li 3-3 ⁇ Y 1+ ⁇ -a Me a Cl 6-x-y Br x I y Formula (8)
  • Me represents at least one element selected from the group consisting of Al, Sc, Ga, and Bi. Further, in Composition formula (8),
  • the negative electrode material according to the first embodiment in the case in which the halide solid electrolyte material satisfies Formula (8), the negative electrode material according to the first embodiment can improve the cycle characteristics of the battery and, in addition, can also improve the charge-discharge efficiency of the battery. Further, since the halide solid electrolyte material that satisfies Formula (8) has high ionic conductivity, a halide reduced form can be efficiently generated.
  • the halide solid electrolyte material in the first embodiment may be a material denoted by Composition formula (9) below. Li 3-3 ⁇ -a Y 1+ ⁇ -a Me a Cl 6-x-y Br x I y Formula (9)
  • Me represents at least one element selected from the group consisting of Zr, Hf, and Ti. Further, in Composition formula (9),
  • the negative electrode material according to the first embodiment in the case in which the halide solid electrolyte material satisfies Formula (9), the negative electrode material according to the first embodiment can improve the cycle characteristics of the battery and, in addition, can also improve the charge-discharge efficiency of the battery. Further, since the halide solid electrolyte material that satisfies Formula (9) has high ionic conductivity, a halide reduced form can be efficiently generated.
  • the halide solid electrolyte material in the first embodiment may be a material denoted by Composition formula (10) below. Li 3-3 ⁇ -2a Y 1+ ⁇ -a Me a Cl 6-x-y Br x I y Formula (10)
  • Me represents at least one element selected from the group consisting of Ta and Nb. Further, in Composition formula (10),
  • the negative electrode material according to the first embodiment in the case in which the halide solid electrolyte material satisfies Formula (10), the negative electrode material according to the first embodiment can improve the cycle characteristics of the battery and, in addition, can also improve the charge-discharge efficiency of the battery. Further, since the halide solid electrolyte material that satisfies Formula (10) has high ionic conductivity, a halide reduced form can be efficiently generated.
  • halide solid electrolyte material in the first embodiment examples include Li 2.7 Y 1.1 Cl 6 , Li 3 YBr 3 Cl 3 , Li3YBr6, Li 2.5 Zr 0.5 Y 0.5 Cl 6 , Li 3 YBr 2 Cl 2 I 2 , Li 3.1 Y 0.9 Ca 0.1 Cl 6 , Li 3 Y 0.8 Al 0.2 Cl 6 , Li 2.5 Y 0.5 Hf 0.5 Cl 6 , Li 2.8 Y 0.9 Ta 0.1 Cl 6 , Li 4.5 Y 0.475 Bi 0.025 Cl 6 , and Li 1.5 Y 1.425 Bi 0.075 Cl 6 .
  • the negative electrode material according to the first embodiment in the case in which the halide solid electrolyte material is the material described above as an example, the negative electrode material according to the first embodiment can improve the cycle characteristics of the battery and, in addition, can also improve the charge-discharge efficiency of the battery. Further, since the material described above as an example has high ionic conductivity, a halide reduced form can be efficiently generated.
  • halide solid electrolyte material in the first embodiment other than the above-described materials, for example, known solid electrolyte materials that satisfy Formula (1) above may be used.
  • a peak top may be present at the value of the diffraction angle 2 ⁇ within the range of greater than or equal to ⁇ a and less than or equal to ⁇ b.
  • the peak of the (220) face of LiX is a peak of the (220) face expressed in Miller index hkl of a rock-salt-type structure having a crystal structure belonging to space group Fm-3m of LiCI, LiBr, Lil, or the like.
  • a halogen having a smaller atomic number is selected as the halogen for determining ⁇ b.
  • ⁇ a is a value of the diffraction angle 2 ⁇ of the peak top of a peak derived from the halide solid electrolyte material and is a value closest to ⁇ b above.
  • the negative electrode material according to the first embodiment can further improve the charge-discharge efficiency of the battery.
  • the peak derived from the halide reduced form shifts from ⁇ a to ⁇ b in accordance with Li occlusion.
  • the peak derived from the halide reduced form shifts from ⁇ b to ⁇ a in accordance with Li release. It is considered that the crystal structure of the halide reduced form shrinks and expands in accordance with Li occlusion and Li release. Therefore, it is conjectured that the negative electrode material containing the halide reduced form improves the charge-discharge efficiency.
  • Li 2.7 Y 1.1 Cl 6 is a halide solid electrolyte material that is used in Example 1 described later.
  • Li 2.7 Y 1.1 Cl 6 is also referred to as "LYC".
  • LYC was produced by the same method as the method described in Example 1. Further, Li 2 S-P 2 S 5 (hereafter also referred to as "LPS") that was a glass-ceramic-like solid electrolyte material was produced by the same method as the method described in Example 2.
  • LPS Li 2 S-P 2 S 5
  • an In-Li alloy was produced by stacking an In metal (thickness of 200 ⁇ m), a Li metal (thickness of 300 ⁇ m), and an In metal (thickness of 200 ⁇ m) in this order to come into contact with LPS in the multilayer body and by subjecting this to pressure forming at a pressure of 80 MPa.
  • An In-Li alloy reference-cum-counter electrode was obtained by arranging a stainless steel pin on the In-Li alloy. Consequently, a bipolar electrochemical cell composed of SUS
  • the inside of the insulating outer cylinder was cut off from the external atmosphere and hermetically sealed by using an insulating ferrule.
  • red-LYC The reduced form of LYC (hereafter referred to as "red-LYC”) was produced under the following condition by using the above-described electrochemical cell.
  • the electrochemical cell was placed in a constant temperature bath at 70°C. Thereafter, a working electrode obtained by applying a current to the electrochemical cell at a current density of current value 0.1 mA/cm 2 and by completing the application of the current when an amount of the current applied reached 1 electron per LYC molecule was taken as a red-LYC (1e charge) sample, and a working electrode obtained by completing the application of the current when an amount of the current applied reached 2 electrons per LYC molecule was taken as a red-LYC (2e charge) sample.
  • a current was applied to the electrochemical cell at a current density of current value 0.1 mA/cm 2 so as to lower the potential of a working electrode to -0.6 V (vs Liln), and the resulting working electrode was taken as a red-LYC (full charge) sample.
  • a current was applied to the electrochemical cell at a current density of current value 0.1 mA/cm 2 so as to lower the potential of a working electrode to -0.6 V (vs Liln), a current was applied in the opposite direction at a current density of current value 0.1 mA/cm 2 , the application of the current was completed when an amount of the current applied reached 1 electron per LYC molecule, and the resulting working electrode was taken as a red-LYC (1e discharge) sample.
  • a current was applied to the electrochemical cell at a current density of current value 0.1 mA/cm 2 so as to lower the potential of a working electrode to -0.6 V (vs Liln)
  • a current was applied in the opposite direction at a current density of current value 0.1 mA/cm 2 so as to increase the potential of the working electrode to 1.9 V (vs Liln)
  • the resulting working electrode was taken as a red-LYC (full discharge) sample.
  • Fig. 1 is a graph illustrating X-ray diffraction patterns of red-LYC samples. The results illustrated in Fig. 1 are on the basis of the measurement by using the following method.
  • a fully automatic multipurpose X-ray diffraction system (SmartLab produced by Rigaku Corporation) was used, and an X-ray diffraction pattern of red-LYC was measured in a dry environment at a dew point of lower than or equal to -50°C.
  • the Cu-K ⁇ 1 ray was used as the X-ray source. That is, the Cu-K ⁇ ray (wavelength of 1.5405 ⁇ , i.e. 0.15405 nm) was used as the X-ray, and an X-ray diffraction pattern was measured by using the ⁇ -2 ⁇ method.
  • each of the peak tops of the X-ray diffraction peaks of red-LYC was present between the peak top position of the X-ray diffraction peak derived from LYC (that is, the position of ⁇ a) and the peak top position of the peak of LiCI (that is, the position of ⁇ b).
  • the peak of LiCI illustrated in Fig. 1 is on the basis of the data (ICSD No. 26909) included in the inorganic crystal structure database (ICSD).
  • the X-ray diffraction peak of red-LYC shifts from the peak top position of the X-ray diffraction peak derived from LYC (that is, the position of ⁇ a) to the peak top position of the peak of LiCI (that is, the position of ⁇ b) in accordance with charging (Li occlusion) and shifts from the peak top position of the X-ray diffraction peak of LiCI to the peak top position of the peak of LYC in accordance with discharging (Li release).
  • the shape of the halide reduced form in the first embodiment may be, for example, the shape of a needle, a sphere, or an elliptical sphere.
  • the shape of the halide reduced form may be particulate.
  • the method for producing the halide reduced form there is no particular limitation regarding the method for producing the halide reduced form, and a known method in which a halide solid electrolyte material can be reduced may be used.
  • the method include an electrochemical technique.
  • an electrochemical cell in which a Li-containing compound is used for the counter electrode and a halide solid electrolyte material is used for a working electrode is prepared.
  • the halide reduced form can be produced by applying a constant current to the resulting cell so as to reduce the halide solid electrolyte material of the working electrode.
  • a conductive auxiliary contained in the negative electrode material according to the first embodiment for example, graphite such as natural graphite and artificial graphite, carbon black such as acetylene black and ketjenblack, conductive fibers such as carbon fibers and metal fibers, carbon fluoride, metal powders such as aluminum, conductive whiskers such as zinc oxide and potassium titanate, conductive metal oxides such as titanium oxide, and conductive polymer compounds such as polyanilines, polypyrroles, and polythiophenes may be used.
  • graphite such as natural graphite and artificial graphite
  • carbon black such as acetylene black and ketjenblack
  • conductive fibers such as carbon fibers and metal fibers
  • carbon fluoride metal powders such as aluminum
  • conductive whiskers such as zinc oxide and potassium titanate
  • conductive metal oxides such as titanium oxide
  • conductive polymer compounds such as polyanilines, polypyrroles, and polythiophenes
  • the conductive auxiliary may contain acetylene black.
  • the conductive auxiliary may be composed of acetylene black alone. In the case in which the negative electrode material according to the first embodiment contains acetylene black as the conductive auxiliary, the charge-discharge efficiency of the battery can be further improved.
  • the negative electrode material according to the first embodiment may further contain a second solid electrolyte material.
  • the charge-discharge efficiency and the discharge capacity of the battery can be further improved.
  • the reduction potential of the second solid electrolyte material with respect to lithium may be lower than the reduction potential of the first solid electrolyte material with respect to lithium.
  • the reduction potential of the second solid electrolyte material with respect to lithium is lower than the reduction potential of the first solid electrolyte material with respect to lithium, the second solid electrolyte material is not decomposed during Li occlusion and Li release of the halide reduced form. Consequently, the negative electrode material according to the first embodiment can ensure favorable ionic conductivity and can improve the charge-discharge efficiency and the discharge capacity of the battery.
  • the reduction potential of the solid electrolyte material with respect to lithium is measured by using, for example, the following method.
  • an insulating outer cylinder SUS foil, a solid electrolyte material, and lithium foil are stacked in this order. This was subjected to pressure forming so as to produce a multilayer body. Subsequently, a stainless steel collector is arranged on the top and bottom of the multilayer body, and a collector lead is attached to each collector. Finally, the insulating outer cylinder is cut off from the external atmosphere and hermetically sealed by using an insulating ferrule so as to produce a reduction potential measurement cell.
  • the resulting reduction potential measurement cell is placed in a constant temperature bath at 25°C.
  • the reduction potential with respect to lithium is measured by performing potential scanning from -0.5 V to 6 V in terms of lithium reference potential at a rate of 5 mV/s on the basis of a cyclic voltammetry measurement.
  • the second solid electrolyte material for example, sulfide solid electrolyte materials and oxide solid electrolyte materials may be used.
  • Li 2 S-P 2 S 5 Li 2 S-SiS 2 , Li 2 S-B2S3, Li2S-GeS2, Li 3.25 Ge 0.25 P 0.75 S 4 , and Li 10 GeP 2 S 12 , and the like may be used.
  • LiX (X: F, CI, Br, or I), Li 2 O, MO q , Li p MO q (M: at least one selected from the group consisting of P, Si, Ge, B, Al, Ga, In, Fe, and Zn) (p, q: a natural number), and the like may be added to them.
  • oxide solid electrolyte materials for example, NASICON-type solid electrolyte materials represented by LiTi 2 (PO 4 ) 3 and element substitution products thereof, (LaLi)TiO 3 -based perovskite-type solid electrolyte materials, LISICON-type solid electrolyte materials represented by Li 14 ZnGe 4 O 16 , Li 4 SiO 4 , and LiGeO 4 and element substitution products thereof, garnet-type solid electrolyte materials represented by Li 7 La 3 Zr 2 O 12 and element substitution products thereof, Li 3 N and H substitution products thereof, Li 3 PO 4 and N substitution products thereof, glass in which a Li-B-O compound such as LiBO 2 or Li 3 BO 3 serves as a base and Li 2 SO 4 , Li 2 CO 3 , or the like is added thereto, and glass ceramic may be used.
  • NASICON-type solid electrolyte materials represented by LiTi 2 (PO 4 ) 3 and element substitution products thereof
  • the second solid electrolyte material may contain the sulfide solid electrolyte material.
  • the second solid electrolyte material may contain Li 2 S-P 2 S 5 .
  • Li 2 S-P 2 S 5 has high ionic conductivity and is stable against reduction. Therefore, the negative electrode material according to the first embodiment containing Li 2 S-P 2 S 5 enables the charge-discharge efficiency and the discharge capacity of the battery to be further improved.
  • the shape of the second solid electrolyte material may be, for example, the shape of a needle, a sphere, or an elliptical sphere.
  • the shape of the second solid electrolyte material may be particulate.
  • Fig. 2 is a schematic sectional view illustrating the configuration of a negative electrode material 1000 that is an example of the negative electrode material in the first embodiment.
  • the shape of the halide reduced form is particulate (for example, spherical)
  • the shape of the second solid electrolyte material is particulate (for example, spherical).
  • the negative electrode 1000 in the first embodiment includes a halide reduced form particle 101, a second solid electrolyte particle 102, and a conductive auxiliary 103.
  • the median diameter of the halide reduced form particles 101 may be greater than or equal to 0.1 ⁇ m and less than or equal to 100 ⁇ m.
  • the median diameter of particles denotes a particle diameter at a cumulative volume of 50% (d50) that is determined from grain size distribution measured by a laser diffraction scattering method on a volume basis.
  • the median diameter of the halide reduced form particles 101 being greater than or equal to 0.1 ⁇ m enables the halide reduced form particles 101 and the second solid electrolyte particles 102 to form a favorable dispersion state in the negative electrode material 1000. Consequently, the charge-discharge characteristics of the battery are improved. Meanwhile, the median diameter of the halide reduced form particles 101 being less than or equal to 100 ⁇ m accelerates lithium diffusion in the halide reduced form particles 101. Consequently, the operation of the battery with a high output is facilitated.
  • the median diameter of the halide reduced form particles 101 may be greater than the median diameter of the second solid electrolyte particles 102. Consequently, the halide reduced form particles 101 and the second solid electrolyte particles 102 can form a favorable dispersion state.
  • the median diameter of the second solid electrolyte particles 102 may be less than or equal to 100 ⁇ m .
  • the median diameter being less than or equal to 100 ⁇ m enables the halide reduced form particles 101 and the second solid electrolyte particles 102 to form a favorable dispersion state in the negative electrode material. Consequently, the charge-discharge characteristics are improved.
  • the median diameter of the second solid electrolyte particles 102 may be less than or equal to 10 ⁇ m.
  • the halide reduced form particles 101 and the second solid electrolyte particles 102 can form a favorable dispersion state in the negative electrode material.
  • the negative electrode 1000 in the first embodiment may include a plurality of halide reduced form particles 101 and a plurality of second solid electrolyte particles 102.
  • the content of the halide reduced form particles 101 and the content of the second solid electrolyte particles 102 in the negative electrode material 1000 in the first embodiment may be equal to each other or may be differ from each other.
  • the negative electrode material in the first embodiment may contain materials other than the halide reduced form, the conductive auxiliary, and the second solid electrolyte material.
  • the negative electrode material in the first embodiment may contain, for example, a negative electrode active material and a binder.
  • a binder materials described as examples of a binder contained in at least one of a negative electrode, an electrolyte layer, and a positive electrode in a second embodiment described later may be used.
  • the negative electrode material in the first embodiment may contain the negative electrode active material that has characteristics of occluding and releasing metal ions (for example, lithium ions).
  • metal materials for example, metal materials, carbon materials, oxides, nitrides, tin compounds, and silicon compounds may be used.
  • the metal materials may be simple metals. Alternatively, the metal materials may be alloys. Examples of the metal materials include lithium metal and lithium alloys.
  • the carbon materials include natural graphite, coke, graphitizing carbon, carbon fibers, spherical carbon, artificial graphite, and amorphous carbon.
  • the negative electrode material in the first embodiment may contain, for example, greater than or equal to 30% by mass of halide reduced form or may contain greater than or equal to 80% by mass.
  • the negative electrode material containing greater than or equal to 30% by mass of halide reduced form enables the energy density of the battery to be sufficiently ensured.
  • the negative electrode material in the first embodiment can improve the charge-discharge efficiency of the battery.
  • the negative electrode material in the first embodiment may contain, for example, less than or equal to 20% by mass of conductive auxiliary or may contain less than or equal to 10% by mass.
  • the negative electrode material containing less than or equal to 20% by mass of conductive auxiliary enables the energy density of the battery to be sufficiently ensured.
  • the negative electrode material in the first embodiment can improve the charge-discharge efficiency of the battery.
  • the negative electrode material in the first embodiment may contain, for example, less than or equal to 70% by mass of second solid electrolyte material or may contain less than or equal to 20% by mass.
  • the negative electrode material in the first embodiment can improve the charge-discharge efficiency of the battery.
  • the negative electrode material according to the first embodiment may be produced by, for example, mixing a reduced form of the halide solid electrolyte material produced in advance, the conductive auxiliary, and the second solid electrolyte material when the second solid electrolyte material is added.
  • the negative electrode material according to the first embodiment may be produced by, for example, mixing the halide solid electrolyte material, the conductive auxiliary, and the second solid electrolyte material, preparing an electrochemical cell in which the resulting mixture serves as a working electrode and a Li-containing compound serves as a counter electrode, and applying a constant current to the resulting cell so as to reduce the halide solid electrolyte material of the working electrode.
  • Fig. 3 is a schematic sectional view illustrating the configuration of a battery in the second embodiment.
  • a battery 2000 according to the second embodiment includes a negative electrode 201, an electrolyte layer 202, and a positive electrode 203.
  • the negative electrode 201 contains the same negative electrode material 1000 as in the first embodiment.
  • the electrolyte layer 202 is arranged between the negative electrode 201 and the positive electrode 203.
  • the charge-discharge efficiency of the battery according to the second embodiment can be improved.
  • the negative electrode 201 may be composed of the negative electrode material 1000 alone in the first embodiment.
  • the charge-discharge efficiency of the battery according to the second embodiment can be further improved.
  • the thickness of the negative electrode 201 may be greater than or equal to 10 ⁇ m and less than or equal to 500 ⁇ m. Setting the thickness of the negative electrode to be greater than or equal to 10 ⁇ m enables a sufficient energy density to be ensured. Meanwhile, setting the thickness of the negative electrode to be less than or equal to 500 ⁇ m facilitates the operation with a high output. That is, the thickness of the negative electrode 201 being appropriately adjusted enables the energy density of the battery to be sufficiently ensured and enables the battery to operate with a high output.
  • the electrolyte layer 202 is a layer containing an electrolyte material.
  • the electrolyte material is, for example, a solid electrolyte material. That is, the electrolyte layer 202 may be a solid electrolyte layer.
  • solid electrolyte material contained in the electrolyte layer 202 for example, halide solid electrolyte materials, sulfide solid electrolyte materials, oxide solid electrolyte materials, polymer solid electrolyte materials, and complex hydride solid electrolyte materials may be used.
  • the same halide solid electrolyte material as the halide solid electrolyte material that is before being reduced to the halide reduced form contained in the negative electrode material according to the first embodiment may be used, or other halide solid electrolyte materials different from the above may be used.
  • Li 2 S-P 2 S 5 Li 2 S-SiS 2 , Li 2 S-B2S3, Li2S-GeS2, Li 3.25 Ge 0.25 P 0.75 S 4 , and Li 10 GeP 2 S 12 , and the like may be used.
  • LiX (X: F, CI, Br, or I), Li 2 O, MO q , Li p MO q (M: at least one selected from the group consisting of P, Si, Ge, B, Al, Ga, In, Fe, and Zn) (p, q: a natural number), and the like may be added to them.
  • oxide solid electrolyte materials for example, NASICON-type solid electrolyte materials represented by LiTi 2 (PO 4 ) 3 and element substitution products thereof, (LaLi)TiO 3 -based perovskite-type solid electrolyte materials, LISICON-type solid electrolyte materials represented by Li 14 ZnGe 4 O 16 , Li 4 SiO 4 , and LiGeO 4 and element substitution products thereof, garnet-type solid electrolyte materials represented by Li 7 La 3 Zr 2 O 12 and element substitution products thereof, Li 3 N and H substitution products thereof, Li 3 PO 4 and N substitution products thereof, glass in which a Li-B-O compound such as LiBO 2 or Li 3 BO 3 serves as a base and Li 2 SO 4 , Li 2 CO 3 , or the like is added thereto, and glass ceramic may be used.
  • NASICON-type solid electrolyte materials represented by LiTi 2 (PO 4 ) 3 and element substitution products thereof
  • the polymer solid electrolyte materials for example, compounds of polymer compounds and lithium salts may be used.
  • the polymer compound may have an ethylene oxide structure. Having an ethylene oxide structure enables a large amount of lithium salt to be contained and enables the ionic conductivity to be further enhanced.
  • the lithium salts LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiSO 3 CF 3 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 C 2 F 5 ) 2 , LiN(SO 2 CF 3 )(SO 2 C 4 F 9 ), LiC(SO 2 CF 3 ) 3 , and the like may be used. At least one lithium salt selected from these may be used alone as the lithium salt. Alternatively, mixtures of at least two lithium salts selected from these may be used as the lithium salt.
  • LiBH 4 -Lil and LiBH 4 -P 2 S 5 may be used.
  • the electrolyte layer 202 may contain a solid electrolyte material as a primary component. That is, the electrolyte layer 202 may contain, for example, greater than or equal to 50% in terms of mass ratio (greater than or equal to 50% by mass) of solid electrolyte material relative to the total of the electrolyte layer 202.
  • the charge-discharge characteristics of the battery can be further improved.
  • the electrolyte layer 202 may contain, for example, greater than or equal to 70% in terms of mass ratio (greater than or equal to 70% by mass) of solid electrolyte material relative to the total of the electrolyte layer 202.
  • the charge-discharge characteristics of the battery can be further improved.
  • the electrolyte layer 202 may contain a solid electrolyte material as a primary component while further containing incidental impurities or starting raw materials used for synthesizing the solid electrolyte material and byproducts, decomposition products, and the like.
  • the electrolyte layer 202 may contain, for example, 100% in terms of mass ratio (100% by mass) of solid electrolyte material relative to the total of the electrolyte layer 202 except incidentally included impurities.
  • the charge-discharge characteristics of the battery can be further improved.
  • the electrolyte layer 202 may be composed of the solid electrolyte material alone.
  • the electrolyte layer 202 may contain at least two of materials listed as the solid electrolyte materials.
  • the electrolyte layer 202 may contain the halide solid electrolyte material and the sulfide solid electrolyte material.
  • the thickness of the electrolyte layer 202 may be greater than or equal to 1 ⁇ m and less than or equal to 300 ⁇ m. In the case in which the thickness of the electrolyte layer 202 is greater than or equal to 1 ⁇ m, there is a low possibility of a short circuit occurring between the negative electrode 201 and the positive electrode 203. Meanwhile, in the case in which the thickness of the electrolyte layer 202 is less than or equal to 300 ⁇ m, the operation with a high output is facilitated. That is, the thickness of the electrolyte layer 202 being appropriately adjusted enables sufficient safety of the battery to be ensured and enables the battery to operate with a high output.
  • the positive electrode 203 contains positive electrode active material particles and solid electrolyte particles.
  • the positive electrode 203 contains a positive electrode active material that has characteristics of occluding and releasing metal ions (for example, lithium ions).
  • metal ions for example, lithium ions
  • lithium-containing transition metal oxides, transition metal fluorides, polyanion materials, fluorized polyanion materials, transition metal sulfides, transition metal oxysulfides, transition metal oxynitrides, and the like may be used.
  • using the lithium-containing transition metal oxide as the positive electrode active material enables the production cost to be reduced and enables the average discharge voltage to be increased.
  • the lithium-containing transition metal oxides include Li(NiCoAl)O 2 , Li(NiCoMn)O 2 , and LiCoO 2.
  • the positive electrode 203 may contain the solid electrolyte material.
  • solid electrolyte material solid electrolyte materials described as examples of the material for constituting the electrolyte layer 202 may be used. According to the above-described configuration, the lithium ion conductivity inside the positive electrode 203 is enhanced and the operation with a high output is made possible.
  • the median diameter of the positive electrode active material particles may be greater than or equal to 0.1 ⁇ m and less than or equal to 100 ⁇ m.
  • the median diameter of the positive electrode active material particles being greater than or equal to 0.1 ⁇ m enables the positive electrode active material particles and the solid electrolyte material to form a favorable dispersion state. Consequently, the charge-discharge characteristics of the battery are improved.
  • the median diameter of the positive electrode active material particles being less than or equal to 100 ⁇ m accelerates lithium diffusion in the positive electrode active material particles. Consequently, the operation of the battery with a high output is facilitated. That is, the positive electrode active material particles having an appropriate size enables the battery having excellent charge-discharge characteristics and being capable of operating with a high output to be obtained.
  • the median diameter of the positive electrode active material particles may be greater than the median diameter of the solid electrolyte material. Consequently, the positive electrode active material particles and the solid electrolyte material can form a favorable dispersion state.
  • volume ratio "v:(100 - v)" of the positive electrode active material particles to the solid electrolyte material contained in the positive electrode 203 (where v represents the volume ratio of the positive electrode active material particles), 30 ⁇ v ⁇ 95 may be satisfied.
  • 30 ⁇ v applies, a sufficient energy density of the battery can be ensured.
  • v ⁇ 95 applies, the operation of the battery with a high output is facilitated.
  • the thickness of the positive electrode 203 may be greater than or equal to 10 ⁇ m and less than or equal to 500 ⁇ m.
  • the thickness of the positive electrode being greater than or equal to 10 ⁇ m enables a sufficient energy density of the battery to be ensured.
  • the thickness of the positive electrode being less than or equal to 500 ⁇ m enables the battery to operate with a high output. That is, the thickness of the positive electrode 203 being adjusted to within an appropriate range enables the energy density of the battery to be sufficiently ensured and enables the battery to operate with a high output.
  • a binder may be contained in at least one of the negative electrode 201, the electrolyte layer 202, and the positive electrode 203.
  • the adhesiveness between particles can be improved by the binder.
  • the binder can improve the binding properties of the materials constituting the electrode.
  • the binder include polyvinylidene fluorides, polytetrafluoroethylenes, polyethylenes, polypropylenes, aramid resins, polyamides, polyimides, polyamide-imides, polyacrylonitriles, polyacrylic acids, polyacrylic acid methyl esters, polyacrylic acid ethyl esters, polyacrylic acid hexyl esters, polymethacrylic acids, polymethacrylic acid methyl esters, polymethacrylic acid ethyl esters, polymethacrylic acid hexyl esters, polyvinyl acetates, polyvinyl pyrrolidones, polyethers, polyether sulfones, hexafluoro
  • copolymers of at least two materials selected from the group consisting of tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, pentafluoropropylene, fluoromethyl vinyl ether, acrylic acid, and hexadiene may be used. At least two selected from these may be mixed and used as the binder.
  • At least one of the negative electrode 201 and the positive electrode 203 may contain a conductive auxiliary.
  • the electron conductivity can be enhanced by the conductive auxiliary.
  • the conductive auxiliary for example, graphite such as natural graphite and artificial graphite, carbon black such as acetylene black and ketjenblack, conductive fibers such as carbon fibers and metal fibers, carbon fluoride, metal powders such as aluminum, conductive whiskers such as zinc oxide and potassium titanate, conductive metal oxides such as titanium oxide, and conductive polymer compounds such as polyanilines, polypyrroles, and polythiophenes may be used. In the case in which carbon conductive auxiliaries are used, the cost can be reduced.
  • the battery in the second embodiment may be constructed as batteries having various types of shapes such as a coin type, a cylindrical type, a square type, a sheet type, a button type, a flat type, a stacked type, and the like.
  • the operation temperature of the battery there is no particular limitation regarding the operation temperature of the battery, and the temperature may be -50°C to 100°C. Higher temperature enables the ionic conductivity of the halide reduced form to be improved and enables the operation with a high output to be facilitated.
  • the battery in the second embodiment may be produced by, for example, preparing each of a material for forming the positive electrode, a material for forming the electrolyte layer, and a material for forming the negative electrode and producing a multilayer body in which the positive electrode, the electrolyte layer, and the negative electrode are arranged in this order by using a known method.
  • the following method can also be used.
  • a multilayer body in which the positive electrode, the electrolyte layer, and a negative electrode precursor layer containing the halide solid electrolyte material in the state before being reduced to the halide reduced form contained in the negative electrode material in the first embodiment are arranged in this order is produced.
  • the positive electrode functions as the counter electrode
  • the negative electrode precursor layer functions as the working electrode so as to reduce the halide solid electrolyte material in the negative electrode precursor layer. Consequently, the battery in the second embodiment including the positive electrode, the electrolyte layer, and the negative electrode that contains the halide reduced form and the conductive auxiliary is obtained.
  • an example of the method for producing the battery according to the second embodiment includes
  • the negative electrode material and the battery according to the present disclosure are not limited to the following examples.
  • LYC and acetylene black (hereafter also referred to as "AB") serving as the conductive auxiliary were weighed at a mass ratio of 90:10. These were mixed in an agate mortar so as to produce a negative electrode material precursor.
  • LYC, LPS, and AB serving as the conductive auxiliary were weighed at a mass ratio of 30:60:10. These were mixed in an agate mortar so as to produce a negative electrode material precursor.
  • LGPS sulfide solid electrolyte material
  • LGPS LGPS
  • LPS LPS
  • AB AB
  • LYC was used alone as the negative electrode material precursor.
  • LYC and LPS were weighed at a mass ratio of 40:60. These were mixed in an agate mortar so as to produce a negative electrode material precursor.
  • an In metal (thickness of 200 ⁇ m), a Li metal (thickness of 300 ⁇ m), and an In metal (thickness of 200 ⁇ m) were stacked in this order on one surface of the solid electrolyte layer opposite to the surface in contact with the negative electrode precursor layer.
  • a stainless steel collector was arranged on the top and bottom of the multilayer body, and a collector lead was attached to each collector.
  • the inside of the insulating outer cylinder was cut off from the external atmosphere and hermetically sealed by using an insulating ferrule.
  • a surface pressure of 150 MPa was applied to the multilayer body composed of the working electrode, the solid electrolyte layer, and the counter electrode by vertically constraining the multilayer body with four volts.
  • the battery was obtained.
  • the halide solid electrolyte material contained in the negative electrode at this stage was in the state before being reduced.
  • a charge-discharge test was performed by using the battery of each of Example 1, Example 2, Comparative example 1, Reference example 1, and Reference example 2 under the following condition.
  • the battery was placed in a constant temperature bath at 25°C.
  • the battery was charged to a voltage of -0.52 V (vs Liln) at a current density of current value 0.1 mA/cm 2 so as to produce a battery including a negative electrode containing a halide reduced form (that is, red-LYC) or a sulfide reduced form (that is, red-LGPS).
  • Example 2 It was ascertained from the results of Example 2 and Comparative example 1 that the compatibility between a high charge-discharge efficiency and a high discharge capacity of the battery can be ensured by using the halide reduced form.
  • Example 1 It was ascertained from the results of Example 1 and Reference example 1 that the charge-discharge efficiency of the battery is improved by adding the conductive auxiliary to the halide reduced form compared with the case of just the halide reduced form.
  • Example 2 It was ascertained from the results of Example 2 and Reference example 2 that the charge-discharge efficiency of the battery is improved by adding the conductive auxiliary to the halide reduced form and the second solid electrolyte material compared with the case of just the halide reduced form and the second solid electrolyte material.
  • the charge-discharge efficiency of the battery is improved by using the negative electrode material containing the reduced form of the first solid electrolyte material denoted by a composition formula Li ⁇ M ⁇ X ⁇ , where each of ⁇ , ⁇ , and ⁇ is a value greater than 0, M includes at least one of metal elements except Li and semimetals, and X represents at least one element selected from the group consisting of CI, Br, I, and F and containing the conductive auxiliary.
  • the battery according to the present disclosure may be used as, for example, all-solid lithium ion secondary batteries.

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